JPH04370159A - Combination filler and epoxy resin composition compounded with the combination filler - Google Patents
Combination filler and epoxy resin composition compounded with the combination fillerInfo
- Publication number
- JPH04370159A JPH04370159A JP5292091A JP5292091A JPH04370159A JP H04370159 A JPH04370159 A JP H04370159A JP 5292091 A JP5292091 A JP 5292091A JP 5292091 A JP5292091 A JP 5292091A JP H04370159 A JPH04370159 A JP H04370159A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- material particles
- resin composition
- particles
- composite filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 35
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 35
- 239000000945 filler Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000007771 core particle Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 25
- 239000011162 core material Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000003566 sealing material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 9
- 238000005452 bending Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 tetraphenylphosphonium tetraphenylborate Chemical compound 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、樹脂を主成分とした例
えば封止用の組成物に有用な複合充填材及びこの充填材
を配合した、封止用に適したエポキシ樹脂組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite filler which is useful in, for example, a sealing composition containing a resin as a main component, and an epoxy resin composition containing this filler and which is suitable for sealing.
【０００２】0002
【従来の技術】近年、高集積４ｂｉｔ、１６ｂｉｔ用Ｌ
ＳＩ用に適した封止材の分野においては、半導体チップ
の大型化にともない耐はんだ性とともに高度な低応力性
が付与された材料の開発が必要とされ、封止材に配合さ
れる充填材による効果が期待されている。低応力化のた
めには、低線膨張率化と低弾性率化が必要であるが、そ
のうち低線膨張率化については、これまで数種の粒子を
複合した複合充填材が有する低い熱膨張性を利用する研
究がなされている。この複合充填材の低線膨張性を実現
するには、例えばＫＥＲＮＥＲ式に基づいたシリカの高
充填化による方法及びシリコーン樹脂変性による手法が
検討されてきたが、いずれも他の粒子の物性とのトレー
ドオフを生じ、今後はさらなる低線膨張率化を目指すに
は、新たな開発が必要である。[Prior Art] In recent years, highly integrated 4-bit and 16-bit L
In the field of encapsulants suitable for SI, as semiconductor chips become larger, there is a need to develop materials that have solder resistance and a high degree of low stress. It is expected that this will have an effect. In order to reduce stress, it is necessary to lower the coefficient of linear expansion and the modulus of elasticity. Research is being done that utilizes gender. In order to achieve low linear expansion of this composite filler, for example, a method of increasing the filling of silica based on the KERNER equation and a method of modifying silicone resin have been investigated, but both methods are based on the physical properties of other particles. This creates a trade-off, and new developments are required in order to aim for even lower linear expansion coefficients in the future.
【０００３】他方粒子表面の改質によるものとして、従
来から広く検討されてきたトポケミカルな改質の他にも
、メカノケミカルな改質、コーティングによる改質、湿
式法でカプセル化する改質、高エネルギー利用による改
質、沈澱反応を利用した改質など多くの手法が検討され
てきた。これらのうちメカノケミカルな改質について着
目したところ、これまで芯材粒子、壁材粒子に有機物、
金属、セラミックを用いた系で検討されており、粒子の
流動性、分散性、電気的特性をはじめ種々の特性の制御
が試みられている。On the other hand, in addition to topochemical modification, which has been widely studied as a modification of the particle surface, there are also mechanochemical modification, modification by coating, modification by encapsulation by wet method, and Many methods have been studied, including reforming using energy and reforming using precipitation reactions. Among these, we focused on mechanochemical modification, and found that so far, organic substances and
Systems using metals and ceramics have been investigated, and attempts have been made to control various properties including particle fluidity, dispersibility, and electrical properties.
【０００４】本発明者等は、これまで成形品の強度を向
上させることを究極の目的として、樹脂組成物中に配合
される複合充填材の強度的性質を向上させる充填材の特
性及びカップリング剤処理を中心に検討し、本発明に到
った。[0004] The present inventors have hitherto developed filler characteristics and coupling that improve the strength properties of composite fillers blended into resin compositions, with the ultimate aim of improving the strength of molded products. The present invention was arrived at after conducting research focusing on chemical treatment.
【０００５】[0005]
【発明が解決しようとする課題】したがって、この発明
の解決する課題は、封止材の強度の向上に有効な複合充
填材及びこの複合充填材を配合した封止用に適したエポ
キシ樹脂組成物を提供する点にある。[Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to provide a composite filler effective for improving the strength of a sealing material and an epoxy resin composition suitable for sealing containing this composite filler. The point is to provide the following.
【０００６】[0006]
【課題を解決するための手段】この発明に係る複合充填
材は、シリカを芯材粒子として用い、この芯材粒子の表
面にエポキシ樹脂を壁材粒子として付着させてカプセル
化した複合充填材であって、かつ壁材粒子が０．１μｍ
〜５μｍで、芯材粒子と壁材粒子の粒径比が８：１以上
で、重量比が１０：１以上である点を特徴とするもので
ある。[Means for Solving the Problems] The composite filler according to the present invention is a composite filler in which silica is used as a core particle and epoxy resin is attached as a wall particle to the surface of the core particle to encapsulate it. and the wall material particles are 0.1μm
~5 μm, the particle size ratio of core material particles to wall material particles is 8:1 or more, and the weight ratio is 10:1 or more.
【０００７】そして他の発明に係るエポキシ樹脂組成物
は、エポキシ樹脂、硬化剤、及び複合充填材を配合して
なるエポキシ樹脂組成物において、上記の複合充填材が
シリカを芯材粒子として用い、この芯材粒子の表面にエ
ポキシ樹脂を壁材粒子として付着させてカプセル化した
複合充填材であって、かつ壁材粒子が０．１μｍ〜５μ
ｍで、芯材粒子と壁材粒子の粒径比が８：１以上で、重
量比が１０：１以上である複合充填材である点を特徴と
するものである。[0007]An epoxy resin composition according to another invention is an epoxy resin composition comprising an epoxy resin, a curing agent, and a composite filler, wherein the composite filler uses silica as a core particle, A composite filler in which an epoxy resin is attached as wall material particles to the surface of the core material particles and encapsulated, and the wall material particles are 0.1 μm to 5 μm.
The present invention is characterized in that it is a composite filler in which the particle size ratio of core material particles to wall material particles is 8:1 or more and the weight ratio is 10:1 or more.
【０００８】以下、この発明を詳しく説明する。複合充
填材を構成する芯材粒子としてのシリカとしては、溶融
シリカが適切である。このシリカの粒径は、１００μｍ
以下０． １μｍ以上が好ましい。その理由は、上限を
越えると、たとえば封止用の樹脂組成物の充填材として
用いた場合、半導体を封止するためにこの樹脂組成物を
成形したときにゲート詰まりを起こしやすく、また樹脂
組成物の流動性が低下し、成形しにくいからである。[0008] This invention will be explained in detail below. Fused silica is suitable as the silica as the core material particles constituting the composite filler. The particle size of this silica is 100 μm
Below 0. The thickness is preferably 1 μm or more. The reason for this is that if the upper limit is exceeded, for example, when used as a filler in a resin composition for sealing, gate clogging is likely to occur when this resin composition is molded to seal a semiconductor; This is because the fluidity of the product decreases, making it difficult to mold.
【０００９】複合充填材を構成する壁材粒子としてのエ
ポキシ樹脂は、たとえばビスフェノールＡ型エポキシ樹
脂、オルソクレゾールノボラック型エポキシ樹脂、ビフ
ェニルタイプのエポキシ樹脂等が用いられる。そして、
このエポキシ樹脂の粒径は、小さくなるほど、芯材粒子
との大きな相互作用に起因する充填材添加の効果を高め
ることができるために、０． １μｍ〜５μｍに制限さ
れ、さらには０． １μｍ〜１μｍの粒子が好ましい。
さらに芯材粒子と壁材粒子との粒径比は、両粒子間で強
い相互作用を有するためには比較的大きな芯材粒子に対
し付着力の高い小さな壁材粒子を用いることが有効であ
り、８：１以上に制限され、さらには１０：１以上が好
ましい。その上に、芯材粒子と壁材粒子の重量比は、１
２：１以上であることが必要で、さらには１５：１以上
に制限するとより効果的である。すなわち、粒径比が上
記以下の場合は、粒子間の相互付着力が弱まり、また重
量比が上記以下の場合は余剰の壁材粒子が生じ、強度の
向上につながらない。The epoxy resin used as the wall material particles constituting the composite filler includes, for example, bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, and the like. and,
The smaller the particle size of this epoxy resin, the more effective the addition of the filler is due to its greater interaction with the core particles. It is limited to 1 μm to 5 μm, and even 0. Particles of 1 μm to 1 μm are preferred. Furthermore, regarding the particle size ratio of core material particles and wall material particles, in order to have a strong interaction between both particles, it is effective to use small wall material particles with high adhesion to relatively large core material particles. , is limited to 8:1 or more, and more preferably 10:1 or more. Moreover, the weight ratio of core material particles and wall material particles is 1
It is necessary that the ratio is 2:1 or more, and it is more effective to limit it to 15:1 or more. That is, if the particle size ratio is less than the above, the mutual adhesion between the particles will be weakened, and if the weight ratio is less than the above, excess wall material particles will be produced, which will not lead to an improvement in strength.
【００１０】芯材粒子の溶融シリカに壁材粒子のエポキ
シ樹脂を付着させるには、既知の機械的混合法を用いる
ことができる。例示すると自動乳鉢による乾式単純混合
法、メカノヒュージョンシステムによる機械化学的表面
融合法、ハイブリダイザーによる高速気流中衝撃法、メ
カノミルによる乾式コーティング法等がある。中でも強
力な剪断力を利用した機械化学的表面融合法と、強力な
衝撃力を利用した高速気流中衝撃法が高メカノエネルギ
ー下で芯材粒子と壁材粒子の相互作用を強め、エポキシ
樹脂のシリカへの効率のよい付着、カプセル化が実現で
きる。A known mechanical mixing method can be used to adhere the epoxy resin of the wall material particles to the fused silica of the core material particles. Examples include a dry simple mixing method using an automatic mortar, a mechanochemical surface fusion method using a mechanofusion system, a high-speed air impact method using a hybridizer, and a dry coating method using a mechano mill. Among them, the mechanochemical surface fusion method that uses strong shearing force and the high-speed air flow impact method that uses strong impact force strengthen the interaction between core material particles and wall material particles under high mechano energy, and improve the performance of epoxy resin. Efficient adhesion to silica and encapsulation can be achieved.
【００１１】シリカからなる上記複合充填材は、エポキ
シ樹脂でカプセル化する前のシリカと比べると、流動性
が大きく向上するとともに疏水性が高まり、その結果樹
脂組成物の成形性と耐水性が改善される。[0011] The above composite filler made of silica has greatly improved fluidity and hydrophobicity compared to silica before being encapsulated with an epoxy resin, and as a result, the moldability and water resistance of the resin composition are improved. be done.
【００１２】上記の如く複合充填材を配合したエポキシ
樹脂組成物は、ロール、ニーダ、バンバリーミキサー等
を用いて混合して得られる。エポキシ樹脂組成物の配合
するエポキシ樹脂の代表的な化合物は、一般に使用され
ているフェノールノボラック型エポキシ樹脂、オルソク
レゾールノボラック型エポキシ樹脂、その他たとえば下
記一般式■で表されたビフェニール型エポキシ樹脂が用
いられる。The epoxy resin composition blended with the composite filler as described above is obtained by mixing using a roll, kneader, Banbury mixer, or the like. Typical epoxy resin compounds used in the epoxy resin composition include commonly used phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and other biphenyl type epoxy resins represented by the following general formula (■). It will be done.
【００１３】[0013]
【化１】[Chemical formula 1]
【００１４】また、硬化剤の一例を示すと、一般に使用
されているフェノールノボラック、クレゾールノボラッ
ク、その他たとえば下記一般式■で示されるジシクロペ
ンタジエン・フェノール重合体が用いられる。Examples of curing agents include commonly used phenol novolaks, cresol novolaks, and other dicyclopentadiene-phenol polymers represented by the following general formula (2).
【００１５】[0015]
【化２】[Chemical 2]
【００１６】そして硬化促進剤としては、たとえば、１
，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７
、トリエチレンジアミン、ベンジルジメチルアミン、ト
リエタノールアミン、ジメチルアミノエタノール、トリ
ス（ジメチルアミノメチル）フェノール等の三級アミン
類；２−メチルイミダゾール、２−エチル−４−メチル
イミダゾール、２−フェニルイミダゾール、２−フェニ
ル−４−メチルイミダゾール、２−ヘプタデシルイミダ
ゾール等のイミダゾール類；トリブチルホスフィン、メ
チルジフェニルホスフィン、トリフェニルホスフィン、
ジフェニルホスフィン、フェニルホスフィン等の有機ホ
スフィン類；テトラフェニルホスホニウムテトラフェニ
ルボレート、トリフェニルホスフィンテトラフェニルボ
レート、２−エチル−４−メチルイミダゾールテトラフ
ェニルボレート、Ｎ−メチルモルホリンテトラフェニル
ボレート等のテトラフェニルボロン塩等がある。[0016] As the curing accelerator, for example, 1
,8-diaza-bicyclo(5,4,0)undecene-7
, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and other tertiary amines; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 - Imidazoles such as phenyl-4-methylimidazole and 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine,
Organic phosphines such as diphenylphosphine and phenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate; etc.
【００１７】必要に応じて配合される離型剤としては、
たとえばカルナウバワックス、ステアリン酸、モンタン
酸、カルボキシル基含有ポリオレフィンなどがあり、ま
た必要に応じて配合される難燃剤としては三酸化アンチ
モン、臭素化フェノールノボラック等一般に使用されて
いる化合物を使用することができる。[0017] As the mold release agent that may be added as necessary,
Examples include carnauba wax, stearic acid, montanic acid, carboxyl group-containing polyolefin, and flame retardants that are added as necessary include commonly used compounds such as antimony trioxide and brominated phenol novolak. Can be done.
【００１８】[0018]
【比較例】表１に記載のシリカ（平均粒径２３μｍ）を
芯材粒子として用い、壁材粒子であるエポキシ樹脂とし
て実施例１と実施例２と実施例３及び比較例２において
はＥＰ−Ｂ−１（平均粒径０． ５μｍ）、実施例４に
おいてはＥＰ−Ｂ−２（平均粒径１μｍ）、比較例３に
おいてＥＰ−ＡＤ（いずれも商品名．住友化学（株）製
）を用い、この芯材粒子に壁材粒子をメカノヒュージヨ
ンシステとハイブリダイザーを併用して、前者は１４０
０ｒｐｍ，１０分、後者は１４０００ｒｐｍ，１０分の
条件で付着させカプセル化し複合充填材を得た。そして
この複合充填材を表１に記載のとおり配合してエポキシ
樹脂組成物とした。ここで樹脂組成物中の主成分である
エポキシ樹脂としては、住友化学（株）製のＥＳＣＮ−
１９５（商品名），硬化剤としてフエノールノボラック
樹脂（商品名タマノール７５２、荒川化学（株）製），
硬化促進剤として北興化学（株）製のトリフエニルホス
フィンを用い、難燃剤として三酸化アンチモン、離型剤
として天然カルナバワックスを用い、これらの配合物を
ミキシングロールで１０分間混練後、粉砕して得た。こ
れを成形温度１７０℃でトランスファー成形して後、さ
らに１７０℃、４時間でアフターキュアを行って成形品
を得た。この成形品の曲げ試験を測定した。なお、曲げ
試験はＪＩＳ規格、Ｋ−６９１１に準処して行い、室温
での曲げ弾性率、曲げ強度を求めた。[Comparative Example] In Examples 1, 2, 3, and Comparative Example 2, silica (average particle size 23 μm) listed in Table 1 was used as the core material particles, and the epoxy resin as the wall material particles was EP- B-1 (average particle size 0.5 μm), EP-B-2 (average particle size 1 μm) in Example 4, and EP-AD (all trade names, manufactured by Sumitomo Chemical Co., Ltd.) in Comparative Example 3. The core material particles are combined with wall material particles using a mechanofusion system and a hybridizer, and the former is 140%
The latter was deposited at 0 rpm for 10 minutes and the latter was deposited at 14,000 rpm for 10 minutes and encapsulated to obtain a composite filler. This composite filler was then blended as shown in Table 1 to form an epoxy resin composition. Here, the epoxy resin that is the main component in the resin composition is ESCN-
195 (trade name), phenol novolac resin as a curing agent (trade name Tamanol 752, manufactured by Arakawa Chemical Co., Ltd.),
Using triphenylphosphine manufactured by Hokko Chemical Co., Ltd. as a curing accelerator, antimony trioxide as a flame retardant, and natural carnauba wax as a mold release agent, these mixtures were kneaded with a mixing roll for 10 minutes and then ground. Obtained. This was transfer-molded at a molding temperature of 170°C, and then after-cured at 170°C for 4 hours to obtain a molded product. A bending test was performed on this molded product. The bending test was conducted in accordance with the JIS standard, K-6911, and the bending elastic modulus and bending strength at room temperature were determined.
【００１９】
単位：配合量（重量部）
線膨張率（Ｅ−５／℃）
曲げ強度（ｋｇｆ／ｍｍ２ ）
曲げ弾性率（ｋｇｆ／ｍｍ２ ）
この物性試験により、本発明の複合充填剤を配合した樹
脂組成物によって与えられる成形品の封止に要求される
曲げ強度、曲げ弾性率及び線膨張率が改善されているこ
とが実施例を比較例に比べることによって明白である。Unit: Blend amount (parts by weight) Coefficient of linear expansion (E-5/°C) Bending strength (kgf/mm2) Flexural modulus (kgf/mm2) According to this physical property test, the composite filler of the present invention was blended. It is clear from comparing the Examples with the Comparative Examples that the bending strength, bending elastic modulus, and linear expansion coefficient required for sealing molded articles provided by the resin compositions are improved.
【００２０】[0020]
【発明の効果】本発明に係る複合充填材及びこの複合充
填材を配合したエボキシ樹脂組成物は、成形品の強度向
上に有効である。Effects of the Invention The composite filler according to the present invention and the epoxy resin composition blended with this composite filler are effective in improving the strength of molded products.
Claims (2)
子の表面にエポキシ樹脂を壁材粒子として付着させてカ
プセル化した複合充填材であって、壁材粒子が０．１μ
ｍ〜５μｍで、芯材粒子と壁材粒子の粒径比が８：１以
上で、重量比が１０：１以上である複合充填材。1. A composite filler in which silica is used as a core material particle, and an epoxy resin is attached to the surface of the core material particle as a wall material particle to encapsulate the material, the wall material particle being 0.1μ.
m to 5 μm, the particle size ratio of core material particles to wall material particles is 8:1 or more, and the weight ratio is 10:1 or more.
配合してなるエポキシ樹脂組成物において、上記の複合
充填材がシリカを芯材粒子として用い、この芯材粒子の
表面にエポキシ樹脂を壁材粒子として付着させてカプセ
ル化した複合充填材であって、かつ壁材粒子が０．１μ
ｍ〜５μｍで、芯材粒子と壁材粒子の粒径比が８：１以
上で、重量比が１０：１以上である複合充填材を配合し
たエポキシ樹脂組成物。2. An epoxy resin composition comprising an epoxy resin, a curing agent, and a composite filler, wherein the composite filler uses silica as core particles, and the epoxy resin is coated on the surface of the core particles. A composite filler that is adhered and encapsulated as wall material particles, and the wall material particles are 0.1μ
An epoxy resin composition containing a composite filler having a particle size ratio of 8:1 or more between core material particles and wall material particles and a weight ratio of 10:1 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5292091A JPH04370159A (en) | 1991-03-19 | 1991-03-19 | Combination filler and epoxy resin composition compounded with the combination filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5292091A JPH04370159A (en) | 1991-03-19 | 1991-03-19 | Combination filler and epoxy resin composition compounded with the combination filler |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04370159A true JPH04370159A (en) | 1992-12-22 |
Family
ID=12928270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5292091A Pending JPH04370159A (en) | 1991-03-19 | 1991-03-19 | Combination filler and epoxy resin composition compounded with the combination filler |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04370159A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11255955A (en) * | 1998-03-10 | 1999-09-21 | Hitachi Ltd | Capsule-type flame retardant and resin composition for semiconductor sealing by compounding the same |
| JP2001342377A (en) * | 2000-05-30 | 2001-12-14 | Nippon Shokubai Co Ltd | Composite particles and manufacturing method therefor |
| JP2010275334A (en) * | 2009-05-26 | 2010-12-09 | Panasonic Electric Works Co Ltd | Process for producing surface treated silica particle, surface treated silica particle, epoxy resin composition and semiconductor device |
| WO2013111345A1 (en) * | 2012-01-23 | 2013-08-01 | 味の素株式会社 | Resin composition |
-
1991
- 1991-03-19 JP JP5292091A patent/JPH04370159A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11255955A (en) * | 1998-03-10 | 1999-09-21 | Hitachi Ltd | Capsule-type flame retardant and resin composition for semiconductor sealing by compounding the same |
| JP2001342377A (en) * | 2000-05-30 | 2001-12-14 | Nippon Shokubai Co Ltd | Composite particles and manufacturing method therefor |
| JP4628519B2 (en) * | 2000-05-30 | 2011-02-09 | 株式会社日本触媒 | Composite particle and method for producing the same |
| JP2010275334A (en) * | 2009-05-26 | 2010-12-09 | Panasonic Electric Works Co Ltd | Process for producing surface treated silica particle, surface treated silica particle, epoxy resin composition and semiconductor device |
| WO2013111345A1 (en) * | 2012-01-23 | 2013-08-01 | 味の素株式会社 | Resin composition |
| JP5413522B1 (en) * | 2012-01-23 | 2014-02-12 | 味の素株式会社 | Resin composition |
| CN104053721A (en) * | 2012-01-23 | 2014-09-17 | 味之素株式会社 | Resin composition |
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